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• W2157905762 abstract "Treatment of the lithium 1-aza-allyl [LiN(R)C(tBu)CHR]2 1, abbreviated as [Li(L¯L')]2, with PCl3 gave in poor yields the trans-P,P′-dichlorodiazaphosphetidine ClPN(R′)P(Cl)N¯R′ 3 (R = SiMe3, R′ = C(tBu)C(H)SiMe3). An improved route to 3 was based on [Cu(μ-LL′)2] and PCl3; but the method of choice involved conversion of 1 into successively the imine RNC(tBu)CHR2 4 (which upon heating gave the isomeric enamine 5) and Cl2PNC(tBu)CHR2 6 and thermolysis of 6, The imine RNC(tBu)CH(R)PPh2 7, obtained from [Li(L¯L')]2 1 and Ph2PCl, was isomerised into the Z-enamine R2NC(tBu)C(H)PPh2 8, which upon irradiation gave a mixture of 8 and its E-isomer 9. Treatment of 7 with R″PCl2 or PCl3 gave the cyclic phosphonium chlorides [Ph2PP(R″)N(H)C(Btu)=C¯H]Cl (10 R″ = Ph, or 11 R″ = Et) or [Ph2PP(Cl)N(R)C(Btu)=C¯H]Cl 12; 12 with AgOSO2CF3 or Na[BPh4] afforded [Ph2PP(Cl)N(R)C(Btu)=C¯H]A (13 A = CF3SO3, or 14 A = BPh4). The enamines RNC(tBu)CH(X)R (15 X = Cl, or 16 X = I) were obtained from 1 and POCl3 or ICl respectively, and the enamine R2NC(Ph)CR2 17 was obtained from the lithium 1-aza-allyl[LiN(R)C(Ph)CR2(THF)] and CF3SO3SiMe3. Compounds 3–17 were characterised by multinuclear NMR spectroscopy and (in most cases) MS; while single crystal X-ray diffraction data are provided for 3 and 10." @default.
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• W2157905762 date "1997-02-01" @default.
• W2157905762 modified "2023-09-23" @default.
• W2157905762 title "The role of lithium 1,3-bis(trimethylsilyl)-1-aza-allyls in phosphorus chemistry" @default.
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• W2157905762 doi "https://doi.org/10.1016/s0022-328x(96)06601-6" @default.
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